1. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer;
(c) a first anthracene that has a light absorption maximum less than about 400 nanometers; and
(d) a second anthracene having the following structure
wherein each of R1 to R10 is independently selected from H, or alkyl, phenyl or alkoxy groups, provided that at least one of R1 to R10 is not H.
2. A photopolymerizable composition comprising:
(a) a cationically polymerizable resin; and
(b) a photoinitiator system for the cationically polymerizable resin, the photoinitiator system comprising:
(i) an iodonium salt;
(ii) a visible light sensitizer;
(iii) a first anthracene that has a light absorption maximum less than about 400 nanometers; and
(iv) a second anthracene having the following structure
wherein each of R1 to R10 is independently selected from H, alkyl, phenyl or alkoxy groups, provided that at least one of R1 to R10 is not H.
3. The photopolymerizable composition according to claim 2, wherein the cationically polymerizable resin is selected from the group consisting of epoxy, oxetane, vinyl ether and spiro-orthocarbonate resins, and combinations thereof.
4. The photopolymerizable composition according to claim 3, wherein the cationically polymerizable resin comprises an epoxy resin.
5. The photopolymerizable composition according to claim 4, wherein the cationically polymerizable resin comprises a silicon-containing epoxy resin.
6. The photopolymerizable composition according to claim 3, wherein the cationically polymerizable resin comprises a blend of a silicon-containing epoxy resin and an epoxy resin that does not contain silicon.
7. The photopolymerizable composition according to claim 2, wherein the iodonium salt is selected from the group consisting of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenyl phenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl)phenyliodonium hexafluoroantimonate, 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.
8. The photopolymerizable composition according to claim 2, wherein the visible light sensitizer is selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof.
9. The photopolymerizable composition according to claim 2, wherein the visible light sensitizer is an alpha-diketone.
10. The photopolymerizable composition according to claim 9, wherein said alpha-diketone is camphorquinone.
11. The photopolymerizable composition according to claim 2, wherein the first anthracene is unsubstituted anthracene.
12. The photopolymerizable composition according to claim 2, wherein the second anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 1,4-dimethoxyanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, and 9,10-diphenyl-2,6-di-tert-butylanthracene.
13. The photopolymerizable composition according to claim 2, wherein the second anthracene is 2-ethyl-9,10-dimethoxyanthracene
14. The photopolymerizable composition according to claim 2, wherein the second anthracene is 9,10-dimethylanthracene.
15. The photopolymerizable composition according to claim 2, wherein the second anthracene is 9,10-diethoxyanthracene.
16. The photopolymerizable composition according to claim 2, wherein the second anthracene is 1,4-dimethoxyanthracene.
17. The photopolymerizable composition according to claim 2, wherein the second anthracene is 9-methylanthracene.
18. The photopolymerizable composition according to claim 2, wherein the second anthracene is 2-ethylanthracene.
19. The photopolymerizable composition according to claim 2, wherein at least one of R1 to R10 is tert-butyl.
20. The photopolymerizable composition according to claim 2, wherein the second anthracene is 2,6-di-tert-butylanthracene.
21. The photopolymerizable composition according to claim 2, further comprising a free-radically polymerizable resin.
22. The photopolymerizable composition according to claim 2, further comprising a hydroxyl-containing material.
23. The photopolymerizable composition according to claim 2, wherein the photopolymerizable composition is a photopolymerizable adhesive.
24. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer; and
(c) an electron donor comprising an alkoxy substituted anthracene.
25. The system of claim 24, further comprising a second electron donor compound having the following formula:
wherein each of R1 to R10 is independently selected from H, alkyl, phenyl or alkoxy groups.
26. A photopolymerizable composition comprising:
(a) a cationically polymerizable resin; and
(b) a photoinitiator system for the cationically polymerizable resin, the photoinitiator system comprising:
(i) an iodonium salt;
(ii) a visible light sensitizer; and
(iii) an electron donor comprising an alkoxy substituted anthracene.
27. The system of claim 26, further comprising a second electron donor having the following formula:
wherein each of R1 to R10 is independently selected from H, alkyl, phenyl or alkoxy groups.
28. The photopolymerizable composition according to claim 26, wherein the cationically polymerizable resin is selected from the group consisting of epoxy, oxetane, vinyl ether and spiro-orthocarbonate resins, and combinations thereof.
29. The photopolymerizable composition according to claim 28, wherein the cationically polymerizable resin comprises an epoxy resin.
30. The photopolymerizable composition according to claim 29, wherein the cationically polymerizable resin comprises a silicon-containing epoxy resin.
31. The photopolymerizable composition according to claim 28, wherein the cationically polymerizable resin comprises a blend of a silicon-containing epoxy resin and an epoxy resin that does not contain silicon.
32. The photopolymerizable composition according to claim 26, wherein the iodonium salt is selected from the group consisting of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenyl phenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl)phenyliodonium hexafluoroantimonate, 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.
33. The photopolymerizable composition according to claim 26, wherein the visible light sensitizer is selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof.
34. The photopolymerizable composition according to claim 26, wherein the visible light sensitizer is an alpha-diketone.
35. The photopolymerizable composition according to claim 34, wherein the alpha-diketone is camphorquinone.
36. The photopolymerizable composition according to claim 26, wherein the alkoxy substituted anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 1,4-dimethoxyanthracene.
37. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer;
(c) a first anthracene and a second anthracene both having the following structure:
wherein for said first anthracene each of R1 to R10 is independently selected from H, alkyl, phenyl, or alkoxy groups, provided that at least one of R1 to R10 is alkoxy, and wherein for said second anthracene each of R1 to R10 is independently selected from H, alkyl, phenyl or alkoxy groups.
38. A photopolymerizable composition comprising:
(a) a cationically polymerizable resin; and
(b) a photoinitiator system for the cationically polymerizable resin, the photoinitiator system comprising:
(i) an iodonium salt;
(ii) a visible light sensitizer; and
(iii) a first anthracene and a second anthracene both having the following structure:
wherein for said first anthracene each of R1 to R10 is independently selected from H, alkyl, phenyl or alkoxy groups, provided that at least one of R1 to R10 is alkoxy, and wherein for said second anthracene each of R1 to R10 is independently selected from H, alkyl, phenyl or alkoxy groups.
39. The photopolymerizable composition according to claim 38, wherein the cationically polymerizable resin is selected from the group consisting of epoxy, oxetane, vinyl ether and spiro-orthocarbonate resins, and combinations thereof.
40. The photopolymerizable composition according to claim 39, wherein the cationically polymerizable resin comprises an epoxy resin.
41. The photopolymerizable composition according to claim 40, wherein the cationically polymerizable resin comprises a silicon-containing epoxy resin.
42. The photopolymerizable composition according to claim 39, wherein the cationically polymerizable resin comprises a blend of a silicon-containing epoxy resin and an epoxy resin that does not contain silicon.
43. The photopolymerizable composition according to claim 38, wherein the iodonium salt is selected from the group consisting of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenyl phenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl)phenyliodonium hexafluoroantimonate, 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.
44. The photopolymerizable composition according to claim 38, wherein the visible light sensitizer is selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof.
45. The photopolymerizable composition according to claim 38, wherein the visible light sensitizer is an alpha-diketone.
46. The photopolymerizable composition according to claim 45, wherein said alpha-diketone is camphorquinone.
47. The photopolymerizable composition according to claim 38, wherein first anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 1,4-dimethoxyanthracene.
48. A photopolymerizable composition according to claim 38, wherein second anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 1,4-dimethoxyanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, and 9,10-diphenyl-2,6-di-tert-butylanthracene.
49. A photopolymerizable dental material comprising the photopolymerizable composition of claim 2, 26 or 38.
50. The photopolymerizable dental material of claim 49 further comprising at least one filler.
51. The photopolymerizable dental material of claim 50, wherein said filler is selected from quartz, submicron silica, and non-vitreous microparticles.
52. The photopolymerizable dental material of claim 49, further comprising at least one adjuvant.
53. The photopolymerization dental material of claim 52, wherein said adjuvant is selected from accelerators, inhibitors, absorbers, stabilizers, pigments, dyes, viscosity modifiers, surface tension depressants and wetting aids, antioxidants
54. A method for preparing a dental restorative or prosthesis, said method comprising:
(a) providing the photopolymerizable dental material of claim 49; and
(b) polymerizing the dental material by exposing it to light of an appropriate wavelength to provide said dental restorative or prosthesis.
55. The method of claim 54, further comprising the step of disposing said material into the mouth of a patient before or after step (b).
56. The method of claim 54, wherein said dental material is irradiated with light for a period of time less than 120 seconds.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A method of manufacturing a semiconductor device comprising:
preparing a semiconductor substrate;
forming a capacitor above the semiconductor substrate, the capacitor comprising a lower electrode containing metal, a multilayer dielectric film, and an upper electrode smaller than the lower electrode and containing metal;
forming the capacitor comprising:
forming a first conductive film to be processed into the lower electrode;
forming a first dielectric film containing tantalum oxide or niobium oxide, a second dielectric film, and a third dielectric film, the second dielectric film being formed on the first conductive film, the first dielectric film being formed on the second dielectric film, the third dielectric film being formed on the first dielectric film, the second dielectric film and the third dielectric film each having a permittivity lower than the first dielectric film;
forming a second conductive film to be processed into the upper electrode on the third dielectric film;
etching the second conductive film, and forming the upper electrode;
etching the third dielectric film, and removing a portion of the third dielectric film, the portion extending outwardly further than a sidewall of the upper electrode; and
etching the first dielectric film, and removing a portion of the first dielectric film, the portion extending from an upper surface of the first dielectric film to a midway depth of the first dielectric film and extending outwardly further than a sidewall of the upper electrode.
2. The method of manufacturing a semiconductor device according to claim 1, wherein each of the second and third dielectric films contains at least one of silicon nitride, aluminum oxide, hafnium oxide, and zirconium oxide as a material.
3. The method of manufacturing a semiconductor device according to claim 1, wherein the metal is titanium or tantalum.
4. The method of manufacturing a semiconductor device according to claim 2, wherein the metal is titanium or tantalum.
5. The method of manufacturing a semiconductor device according to claim 1,
wherein the second conductive film is etched using a fluorine-base gas,
the third dielectric film is etched using a chlorine-based gas, and
the first dielectric film is etched using a mixture gas of a fluorine-base gas and an oxygen gas.
6. The method of manufacturing a semiconductor device according to claim 2,
wherein the second conductive film is etched using a fluorine-base gas,
the third dielectric film is etched using a chlorine-based gas, and
the first dielectric film is etched using a mixture gas of a fluorine-base gas and an oxygen gas.
7. The method of manufacturing a semiconductor device according to claim 1, further comprising etching the first dielectric film, the second dielectric film, and the first conductive film and forming the lower electrode.
8. The method of manufacturing a semiconductor device according to claim 2, further comprising etching the first dielectric film, the second dielectric film, and the first conductive film and forming the lower electrode.
9. The method of manufacturing a semiconductor device according to claim 1, further comprising forming a fourth dielectric film having a permittivity lower than the first dielectric film.
10. The method of manufacturing a semiconductor device according to claim 2, further comprising forming a fourth dielectric film having a permittivity lower than the first dielectric film.